Salts of tertiary n-di-alkyl derivatives of long chain amines



, Patented. Dec.

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UNITED ,STA

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new products 367,632 filed May 31, 1929, of which this is a continuation in part, I disclose the preparation of new compounds possessing qualities which make them very desirable as wetting, cleansing and emulsifying agents.

1o In general such materials are eifective .same holds aqueous solutions.

' ably selected, possess largely on account of their effect on the interfacial tension between water and an oily or greasy surface. The magnitude of this of fact appears to depend on (a) the presence of certain groups in the molecule and (b) on the shape and general configuration of the molecule. By taking these factors into'consideration I have discovered a series of substances which possess the above-named properties in a remarkable degree. I

It is well known that ammonia and organic substituted ammonias such as the meth-. ylamines have cleansing pro rties. These almost entirely disappear owever when these substances are converted into. their salts, with, for-example, the mineral acids. Thus a solution of ammonium chloride has practically no cleansing properties, and the for methylamine hydrochloride. Further up the homologous series n-amylamine is found to have considerable wetting. properties while the corresponding hydrochloride is a very feeble wettingagent; In general the salts of such amines are far inferior in cleansing properties to the amines themselves. y

I have now discovered a new series of compounds, the salts of tertiary .alkylamines, which, provided the alkyl groups are suitto a large degree the property of reducing the surface tension of To secure this efiect I prepare a tertiary alkyl amine in which one alkyl radical consists ofa long, carbon: chain fully saturated with hydrogen, while the other two alkyl radicals have no more than four carbon atoms each. The degree of Wetting which may be secured at low concentrations of these materials de ends, other thingsbeing equal, on the lengt of the long cleansmg and Application flied June as, 1980.- Serial no. 46am.-

chain. 1 By preparation of representative members of an extensive series I have found that with'along chain of seven carbon atoms the resulting solutions have feeble wetting properties, with a chain of eight carbon 5 atoms the wetting properties are decidedly increased, withtwelve they are still better and this improvement is ma'ntained up to fifteen carbon atoms.

While the initial experiments were concc fined to straight chaincompounds I have now discovered that branched chain compounds are, also useful, provided the n mber of carbon atoms directly connected. falls,

within the limits outlined above. For example, amine salts of this typev derived from dicapryl alcohol are vevy useful.

' For members at any one'length' of long chain, maximum reduction of surface tension is secured by having the two short'chain radicals as small as possible, hat is, methyl groups, but others are good. 'A further de-; velopment in the case of the short chain radicals is the discovery that hydroxy derivatives off the alkyl radicals may also be used to good e ect.

These materials may be prepared by heating the halogen derivative correspondillig to the long chain alkyl radical with the -din-alkygl amine selected; or the primary amine correspondin to the long chain alkyl ical may bewal ylated by any of the standard methods. The salts are formed by neutralizationwith the acid chosen.' The common mineral acids are most convenient, but the soluble organic acids such as acetic, oxalic,

citric may, also be utilized. These salts are solids, generally of soap-like appearance. In some cases they maybe prepared in crystalline form recrystallization from organic solvents. hey give aqueous solutionswhich foam readily and have 'wetting qualities'at large dilutions. They are hence useful in the textile industry in I washing,'cleansing and wetting out being especially valuable in acid baths, and also in I dispersing of certain dyestuffs. These solutions possess powerful emulsifying qualities for oils, andare valuable, for instance, in I fatliquoring df leather. They have the prop-- erty of'forming insoluble lakes with many Product is grams lauryl bromide, 65 grams di-nbutylamine, are warmed up, to ether under,

reflux condenser for 3 hours. eaction occurs very readily and almost completely. diluted with a large volume of water, and-made acid. On ether extraction the bulk of the N -di-n-butyl lauryl amine salt goes into the ether, and on distilling oil the ether a completely water soluble product is obtained- Example 2. N diethanollaarylamiwe sulphate 50 grams laug'yl bromide, 110 grams diethanolamine, are warmed up together under reflux condenser for 7 hours, when a test drop salt thus obtained from the solution gives aclear solution in acidified water.- In this case the reaction proceeds practically to completion. The mixture is diluted with water, and extracted in alkaline state with ether. The ether layer is washed with water to remove the excess of diethanolamine dried, and the ether distilled ofi'. The free base is neutralized with the calculated amount of sulphuric acid. The

Water.

Example 3-. N-llz'etk'yld laapryl oxalate 39 grams dicaprylbromide obtained from crude dicapryl alcohol, and boiling at 165 to 180 C. at 5 mm. pressure are mixed with $8 grams diethylamine and warmed up toether' under reflux'condenser for 13 hours.

he product is poured into alkaline water and extracted with ether. The ether extract is Washed thoroughly, then acidified, and the acid solution made very dilute to take up nearly all the desired amine salt. After separation the aqueous layer is made basic, and

extracted with ether. The ether extract is dried, the ether distilled ofi, and the product vacuum distilled. The portion boiling at 146.5 to 150G. at 2 mm. pressure is collected. By neutralization in acetone solution with the calculated amount of oxalic acid and evaporation the pure salt is obtained.

It is understood that myinvention is not confined to. preparation of the compounds by the above methods nor to the materials mentioned. since. the examples. are merely illustrative of the preparation of a representative number-of members in the series.

is completely soluble in I claim:

- 1. As new products the salts of amines of the general type R where R represents an alkyl radical containing from 9 to 15 carbon atoms directly connected in a'straight chain,-R and R represent radicals of not more than 4 carbon atoms of the class consisting of alkyl and hydroxy alkyl roups. p

2. s new products the salts of amines of the general type v.

at where Rrepresents an alkyl radical containing from 9 to 15 carbon atoms directly connected in a straight chain, R and R represent alkyl radicals containing not more than 4: carbon atoms.

3. As new products the salts of amines of the'general type V 7 R2 where R represents the dicapryl radical, R andR represent alkyl groups of not more than 2 carbon atoms.

4. As new products the salts of amines of the general type where R represents the dicapryl radical, R and R represent ethyl groups.

5. As new products the salts of N-di-ethyldicapryl amine. As a new oxalate.

7. As a new amine sulphate.

In testimony whereof I affix my signature.

TAN O. SOMERVILLE.

product N-di-ethyldicapryl product N -di-\ethanollauryl- 

